2,882,231

United States Patent Office Patented Apr. 14, 1959

2
their use can lead to a decrease in the efficiency in the
operation of knitting machinery due to their tendency to
2,882,231 flake or dust during the knitting operation. This results
NEEDLE OL in size build-up on the needles. The attendant abrasive
effect produces end breakage of the threads or yarn, or
Elmer W. Brennan, Carpentersville, and John N. Bowden, tearing of the fabric, which slows down the production
Crystal Lake, Ill., assignors to The Pure Oil Company, and produces fabrics susceptible to rejection.
Chicago, Ill., a corporation of Ohio It is therefore an object of this invention to provide a
No Drawing. Application November 17, 1954 compounded lubricating oil which will function to effec
Serial No. 469,537 O tively lubricate and provide rust protection for the needles
4 Claims. (C. 252-37.5)
employed in knitting machines. It is also an object of
this invention to formulate a needle oil composition which
has low surface tension, is resistant to oxidation, possesses
good scourability and prevents build-up of polyvinyl
This invention relates to the lubrication of textile ma s alcohol-containing sizing on the needles used in the manu
chinery. It is specifically concerned with a compounded facture of the fabric. -
needle oil for use in the lubrication of knitting machine These and other objects will be made more apparent by
needles. the following detailed description of the instant invention.
In the manufacture of cloth from natural or synthetic
filaments one of the manufacturing techniques employed 20 tionIt has been found that the objects of the instant inven
may be effectuated by the use of an oleaginous com
is knitting wherein knitted fabrics are formed by inter position, preferably comprising a light mineral oil base,
lacing a single yarn or thread in a series of loops by means which has enhanced surface activity, and moisture-rusting
of needles. The fabric may be knitted in either a flat, or preventative characteristics, containing an oil-soluble size
a tubelike cloth by means of circular or flat knitting accumulation inhibitor selected from the group of plas
machines. In each instance, the needles which form the ticizers for vinyl compounds, such as the acyclic and
series of loops are reciprocatively mounted in a needle cyclic esters of phosphoric acids, dicarboxylic acids having
bar installed on the knitting machine. To facilitate their 6 to 10 carbon atoms per molecule, mono-basic aliphatic
operation, the needles are lubricated by a needle oil which acids having 8 to 18 carbon atoms per molecule, and
is applied directly to the needles by suitable means such others.
as a lubricant-saturated felt or a spray applicator. The 30 The preferred oleaginous base material which is em
needle oil is primarily a lubricant for the knitting needles. ployed in the subject composition comprises a light min
However, it must be formulated to meet the requirements eral oil having a viscosity in the range of about 65 SUS
of the particular service in which it is being used. Be to 150 SUS at 100 F. and preferably with a viscosity in
cause of the environment in which the lubricant is em the range of 80–90 SUS at 100 F. The mineral oil may
ployed it is necessary that the oil possess a number of 35 be derived from a paraffin, naphthene or mixed base
additional characteristics in addition to lubricity. For crude oil which, upon being subjected to conventional or
example, the needle oil must provide rust protection for solvent refining techniques, will yield a lubricating oil
the needles. It must have a low surface tension and have fraction having the desired viscosity characteristics. The
a high resistance to oxidation. In addition, the com desired viscosities may be obtained by the use of single
pounded oil must have good scourability in order that any 40 fractions, or blends of several different fractions. Light
oil which is retained on the fabric after the knitting colored stocks, having an NPA color of about 1%, are
process may be readily removed. preferred, in order to minimize the staining of the finished
Filaments, such as threads or yarns, fed to the knitting product. So-called synthetic lubricating oils having these
machines are generally pretreated with a composition properties may also be employed.
having cohesive properties which, inter alia, increases the 45 The refining processes employed in the production of
natural strength of the fabric and gives it temporary pro mineral oils of these characteristics from various crude
tection during the knitting process. This composition, petroleum oils such as Van Zandt, Mid-Continent, and
which is known as sizing, also functions to: others, generally produce a light oil which has a natural,
Prevent abrasion during winding and twisting, high resistance to oxidation. However, if mineral oils
Provide pliability and softness, 50 of this nature canont be readily obtained it may be
Provide protection for the filaments, necessary to supplement the mineral oil composition by
Provide protection from changes in humidity, the addition of a conventional oil-soluble oxidation in
Provide a means to hold or set the twist. hibitor. This expedient is deemed necessary in such in
stances
After the knitting operation the sizing is removed by 55 cation of because compounded oils employed in the lubri
design in a desizing operation, or, incidentally, during exposed to automatically
an environment
operated knitting needles are
conducive to oxidation. In
further processing of the knitted cloth, as, for example, view of the necessary characteristics of this compounded
in a dye bath. In the formulation of sizes, polyvinyl
alcohols are frequently used. One conventional method be employed preferably be clear in color inhibitor
needle oil, it is obvious that the oxidation
to
to
forestall
of synthesizing polyvinyl alcohols involves the hydrolysis any inadvertent staining of the finished fabric. Suitable
of polyvinyl acetate. As a result the properties of the 60 inhibitors include but are not limited to phenyl beta
polyvinyl alcohol is governed by the degrees of polymer naphthylamine, butyl dithiocarbamate, tetramethyldiami
ization and hydrolysis. The partially or completely hy modiphenylmethane, di-tertiary-butyl paracresol, trialkyl
drolyzed grades may be used on fibers such as viscose and phosphites, and others.
cotton, whereas the less absorbent, smooth-surfaced fila Improvement in the surface activity of the mineral
ments such as acetate and nylon require the use of the 65 oil base, if necessary, may be obtained by the use of any
partially hydrolyzed grades. For example, one widely oil-soluble, nonionic surface-active agent which will
used composition known as PM-90 contains 90.4% water, substantially reduce the interfacial tension of the com
8.0% low viscosity, "partially hydrolyzed' polyvinyl alco pounded oil. It is preferred that a surface-active agent
hol and 1.6% boric acid. While these polyvinyl-alcohol
containing sizes function to improve the yarn or thread 70 be employed which will reduce the interfacial tension of
the composition to less than about 10 dynes/cm. Suit
properties and facilitate their being knit into a fabric, able materials which are satisfactory for this use in
 2,882,281
3 4.
clude the oil-soluble products obtained by the conden glycidyl oleate, tributoxy ethyl phosphate, diethylene
sation of fatty substances and their derivatives with ethyl glycol dibenzoate, methyl pentachlorostearate, dioctyl
ene oxide, as well as the oil-soluble products obtained tetrahydrophthalate. In general, 0.5 to 5.0% by weight,
by the condensation of phenolic compounds having side and preferably 1-2% by weight, based on the total com
chains with ethylene oxide. Examples of nonionic agents position of vinyl plasticizer, will suffice to inhibit or
which may be employed in the compounded oil include mitigate the accumulation of polyvinyl alcohol-containing
but are not limited to sorbitan trioleate, diethylene glycol size. However, amounts outside this range may be used.
stearate, diethylene glycol monolaurate, glyceryl mono While separate additives may be employed to impart
oleate, polyoxyethylene sorbitan monolaurate, polyoxy to the mineral oil each of the necessary characteristics,
ethylene sorbitan tristearate, polyoxyethylene sorbitan O the instant invention may be carried out by taking
monooleate, polyoxyethylene sorbitol laurate, polyoxy advantage of the multifunctional characteristics of several
ethylene sorbitol oleate-laurate, polyoxyethylene esters of the foregoing additives. For example, sorbitan mono
of mixed fatty and rosin acids, polyoxyethylene lauryl oleate may be used to improve the rust preventative
alcohol, polyoxyethylene sorbitol cotton seed oil deriva properties as well as substantially lower the interfacial
tive, polyoxyethylene sorbitan trilaurate, polyoxy 5 tension; ditolyl phosphate, while functioning as a size
ethylene sorbitol esters of mixed fatty and rosin acids, accumulation inhibitor, will also serve to enhance the
etc. A number of the foregoing substances marketed rust preventative properties of the compounded oil. These
under various marks may be obtained from the Atlas are only suggested multifunctional additives. Others will
Powder Company. In this regard, reference is made occur to those skilled in this art and will facilitate the
to the brochure entitled Atlas Surface Active Agents, 20 blending of the subject needle oil.
1948, published by the Atlas Power Company. A specific example of a composition of this invention
Other oil-soluble surface-active agents which are ap which has given excellent performance in the lubrication
plicable in carrying out the instant invention are the of knitting needles is as follows:
condensation products of ethylene oxide and an alkyl Component: Amount, percent
phenol. Such compounds, which contain a plurality 25 A neutral mineral lubricating oil having a viscosity
of ethenoxy groups of varying length, include Triton of 85 SUS at 100 F. -------------------- 98.45
X100, Triton X45, etc., marketed by the Rohm & Haas Tricresyl phosphate ------------------------ 1.25
Co. Oil-soluble polyoxyethylene lauryl alcohol ---- 0.25
The foregoing surface-active agents function not only Zinc naphthenate (8% Zn) ------------------ 0.05
to reduce the interfacial tension of the composition, 30
thereby improving the distribution of the oil on the 100.00
knitting needle, but also serve to improve the scour
ability of the composition, facilitating its removal from Various tests characteristic of this particular composi
the knitted fabric. tion are:
In order to provide the necessary rust protection for 35 Carbon residue, percent W. -------------------- 0.02
the needles a conventional rust inhibitor is incorporated Color, NPA --------------------------------
in the needle lubricant of this invention. Typical additive Flash, F. -------------------------------- 395
compositions utilized to combat moisture-rusting are the Fire, F. ---------------------------------- 430
various metal soaps of high molecular weight fatty Gravity, API ------------------------------ 34.9
acids, esters of naphthenic acids or acids derived from 40 Pour point, F. ----------------------------- -10
the oxidation of petroleum fractions, degras or wool Viscosity, SUS, 100 F. ---------------------- 83.9
grease, or the sodium salts of petroleum sulfonic acids. Viscosity, SUS, 130 F. ---------------------- 57.9
In the preparation of the composition of this inven Viscosity, SUS, 210 F. ---------------------- 38.1
tion the foregoing agents are added to the mineral oil Viscosity index --------------------------- - 103
base in order to impart the necessary functional char Neutralization No. (1948) -------------------- 0.03
acteristics to the compounded oil. However, in order Saponification No. --------------------------- 1.5
to prepare a blended oil which will satisfactorily carry Interfacial tension, dynes/cm. ---------------- 3
out the objectives of the instant invention, it is essential Phosphorus, percent W. ---------------------- 0.07
that an additive be employed which will function to pre Sulfur, percent W. --------------------------- 0.
vent accumulation or build-up of size on the knitting Other suitable compositions may be blended by using
needles. It has been found that size build-up can be the following formulae:
prevented by the addition of a plasticizer for vinyl com
pounds. Included in this functional class are cyclic and Component: Amount, wt. percent
acyclic esters selected from the group consisting of the Neutral mineral lubricating oil having a vis
esters of phosphorus acids, dibasic aliphatic and aromatic 55 cosity of 80 SUS at 100 F. ------------ 97.75
organic acids having 6 to 10 carbon atoms per molecule, Tricresyl phosphate ------------------- -- 2.00
and monobasic aliphatic acids having 8 to 18 carbon atoms Alkylphenolethylene oxide condensate . (Dis
per molecule. The alkoxy substituent or substituents of persant N-0------------------------- 0.25
the ester molecule should contain not more than about 10
carbon atoms per molecule. Prominent members of 60
Neutral mineral lubricating oil having a vis
the various family groups include but are not limited to cosity of 100 SUS at 100 F. ------------ 98.20
tricresyl phosphate, triphenyl phosphate, dibutyl phthal Dimethyl phthalate --------------------- 1.50
ate, dicapryl phthalate, diethyl phthalate, di(2-methoxy Alkylaryl polyether alcohol (Triton X-45) - 0.25
ethyl) phthalate, di(methyl Cellosolve) phthalate, di Zn Naphthenate (8% Zn) ---------------- 0.05
methyl phthalate, di-(2-ethylhexyl) phthalate, di-n-octyl Neutral mineral lubricating oil having a vis
phthalate, diisooctyl phthalate, octyl decyl phthalate, cosity of 65 SUS at 100 F. ------------ 98.0
di(2-ethylhexyl adipate), diiso-octyl adipate, butyl oleate, Methyl acetyl ricinoleate ---------------- 1.
glyceryl trioleate, dibutyl sebacate, di(2-ethylhexyl) Sorbitan oleate -------------------------- 0.5
sebacate, butyl stearate, glycol esters of ethylhexoic acid, The formulation of this invention provides a knitting
pelargonic acid, and vegetable oil fatty acids, ricinoleic 70 needle oil which not only provides the necessary lubri
and acetylricinoleic acid esters such as methyl acetyl cation for the knitting needles but also protects them
ricinoleate, butyl acetyl ricinoleate, and propylene glycol from rust and other corrosion. The compounded oil is
diacetyl ricinoleate. oxidation resistant, has a low interfacial tension, good
Other illustrative examples of plasticizers include scourability for easy removal of the oil from the textile
epoxidized fatty acid esters such as butyl epoxystearate, 75 fabric, and prevents polyvinyl-alcohol-containing sizes
 2,882,281
5 6
from adhering to and accumulating upon the knitting (2) an oil-soluble, non-ionic, surface active agent selected
needles, thereby eliminating the inimical effects of size from the group consisting of polyoxyethylene esters and
accumulation. ethers in an amount sufficient to reduce the interfacial
Accordingly, we claim as our invention: tension of the compounded oil to less than about 10
1. A compounded knitting needle oil especially adapt dynes/cm., and (3) about 0.5-50% by weight, based on
able for use in the lubrication of machine-operated knitting total composition, of an oil-soluble, plasticizer for poly
needles in the knitting of yarn or thread pretreated with vinyl compounds selected from the group consisting of
a polyvinyl alcohol-containing size into fabric, said oil esters of phthalic acid containing no alkoxy substituent of
consisting of a major portion of a petroleum oil having more than 10 carbon atoms, to prevent the accumulation
a viscosity of about 65-150 SUS G 100 F. and small 0 of said size on said knitting needles.
portions of (1) an oil-soluble rust inhibitor in an amount 3. A needle oil in accordance with claim 1 in which
sufficient to inhibit the moisture rusting of said needles, the ester of phthalic acid is dioctyl phthalate.
(2) an oil-soluble, non-ionic surface active agent in an 4. A needle oil comprising neutral mineral lubricat
amount sufficient to reduce the interfacial tension of the ing oil in the amount of 98.20% by weight, 1.50% by
compounded oil to less than about 10 dynes/cm., and 15 weight of dimethyl phthalate, 0.25% by weight of an
(3) about 0.5-50% by weight, based on total composi alkylary polyether alcohol and 0.5% by weight of zinc
tion, of an oil-soluble, ester plasticizer for polyvinyl naphthenate.
compounds selected from the group consisting of esters
of phthalic acid containing no alkoxy substituent of References Cited in the file of this patent
more than 10 carbon atoms, to prevent the accumulation 20 UNITED STATES PATENTS
of said size on said knitting needles.
2. A compounded knitting needle oil especially adapt 2,332,825 Zimmer -------------- Oct. 26, 1943
able for use in the lubrication of machine-operated knitting 2,415,353 Johnston -------------- Feb. 4, 1947
needles in the knitting of yarn or thread pretreated with 2,446,944 Morgan -------------- Aug. 10, 1948
a polyvinyl alcohol-containing size into fabric, said oil 25 2,470,405 Leland ---------------- May 17, 1949
consisting of a major portion of a petroleum oil having 2,677,700 Jackson ---------------- May 4, 1954
a viscosity of about 65-150 SUS GD 100 F. and small 2,690,426 Jefferson -------------- Sept. 28, 1954
portions of (1) an oil-soluble, metal soap of a high FOREIGN PATENTS
molecular weight fatty acid rust inhibitor in an amount
sufficient to inhibit the moisture rusting of said needles, 30 694,425 Great Britain ---------- July 22, 1953